JP2001354724A - Alpha-olefin/aromatic vinyl compound copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel α-olefin/aromatic vinyl compound copolymer low in an extent of alternative copolymerization and high in an extent of block copolymerization, especially on the aromatic vinyl compound. SOLUTION: There is provided an α-olefin/aromatic vinyl compound copolymer obtained by copolymerization by using a transition metal compound represented by formula (1) and a cocatalyst component [wherein A1 and A2 are each cyclopentadienyl, a substituted cyclopentadienyl, or the like; Y1 and Y2 are each a substituted or unsubstituted alkylene or the like; provided that at least either of them is a substituted or unsubstituted alkylene; M1 is titanium or the like; and X1 and X2 are each hydrogen, a halogen, or the like].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an α-olefin-
The present invention relates to an aromatic vinyl compound copolymer. More specifically, the present invention relates to a novel α-olefin-aromatic vinyl compound copolymer having a low alternating property and a high blocking property, particularly a high blocking property caused by an aromatic vinyl compound.

[0002]

2. Description of the Related Art Hitherto, in the production of α-olefin-aromatic vinyl compound-based copolymers such as ethylene-styrene copolymers, a method of copolymerizing with a Ziegler-Natta catalyst has been studied. There were drawbacks that the polymerization activity was not sufficient, the copolymerizability was low, and only those containing a large amount of the homopolymer were obtained.

On the other hand, recently, as a catalyst component, (1) a method using a metallocene compound or a crosslinked diphenoenoxy compound, and (2) a method using an aluminoxane or a borate compound have been proposed. For example, JP-A-3-25
007, JP-A-6-49132, JP-A-7-278230, JP-A-8-269134, JP-A-9-40709, and JP-A-9-1838
09, JP-A-9-302014, JP-A-9-302014
309925 and Japanese Patent No. 2684154. When these catalysts are used, the polymerization activity per transition metal in the production of an ethylene-styrene copolymer is extremely high, and a copolymer having a narrow molecular weight distribution can be obtained, but the copolymer has a high alternating property. Although it was rich in flexibility, it had low elastic modulus and low breaking strength, and had poor mechanical strength. As described above, in the ethylene-styrene copolymer, it has been required to further improve the mechanical strength and to sufficiently bring out the properties of the comonomer. In order to satisfy the above requirements, there has been a demand for a method for producing a copolymer having a low alternating property and a high block property.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems in the α-olefin-aromatic vinyl compound-based copolymer, and has a low alternating property and a high blocking property. It is an object of the present invention to provide a novel α-olefin-aromatic vinyl compound copolymer having a high blocking property with respect to an aromatic vinyl compound.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a catalyst comprising a combination of a transition metal compound having a specific chemical structure and a co-catalyst component has been developed. The inventors have found that the block copolymerizability of an α-olefin and an aromatic vinyl compound is excellent, and have completed the present invention based on these findings. That is, the gist of the present invention is as follows.

[1] A copolymer comprising an α-olefin and an aromatic vinyl compound, wherein the content of the aromatic vinyl compound is 0.1 to 90 mol% and the molecular weight distribution measured by the GPC method is 3.0. And the signal (Sβδ) based on the (aromatic vinyl compound-olefin-olefin) chain and the signal (Sββ) based on the (aromatic vinyl compound-olefin-aromatic vinyl compound) chain in ¹³ C-NMR measurement And a signal (Tββ) based on a block chain of an aromatic vinyl compound (aromatic vinyl compound−aromatic vinyl compound−aromatic vinyl compound), and a block chain of an olefin portion (olefin−olefin−olefin). Olefin), and a signal of the aromatic vinyl compound component represented by the following relational expression: Index indicating lockability (θ)
Is an α-olefin-aromatic vinyl compound copolymer having a content of 10 to 80 (%).

[0007]

(Equation 2)

[Wherein I (Tββ + Tβδ) is ¹³ C
In NMR measurement, the sum of the intensities of the signals Tβ and Tβδ is shown. Here, Tβδ indicates a signal based on a (aromatic vinyl compound-aromatic vinyl compound-olefin) chain. I (Tδδ + Tγδ + Tββ + Tβδ)
Indicates the sum of the respective intensities of the signals Tδδ, Tγδ, Tββ, and Tβδ based on all the chains involving the aromatic vinyl compound component in the chains of the copolymer in ¹³ C-NMR measurement. Here, Tδδ is a signal based on a (olefin-aromatic vinyl compound-olefin) chain, and Tγδ is a signal based on a heterogeneous bond of an (aromatic vinyl compound-aromatic vinyl compound-olefin-olefin) chain or (aromatic vinyl compound). -Olefin-
2 shows a signal based on a heterogeneous bond in an (aromatic vinyl compound-olefin) chain. [2] The α-olefin-aromatic vinyl compound copolymer according to [1], wherein the aromatic ring in the chain of the aromatic vinyl compound component in the copolymer is atactic.

[3] The above [1] or [1] wherein an α-olefin and an aromatic vinyl compound are copolymerized in the presence of a polymerization catalyst comprising (A) a transition metal compound component and (B) a cocatalyst component. 2] The α-olefin-aromatic vinyl compound copolymer described in [2].

[4] In addition to the components (A) and (B) in the above [3], a catalyst component (C)
The α-olefin-aromatic vinyl compound copolymer according to the above [3], wherein a polymerization catalyst obtained by adding an alkylating agent is used.

[5] The above-mentioned [3] or [4], wherein the component (A) in the polymerization catalyst is a transition metal compound represented by the following general formula (1), (2) or (3).
The α-olefin-aromatic vinyl compound copolymer described in the above.

[0012]

Embedded image

[In the formula (1), A ¹ and A ² each independently represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group;
Y ¹ and Y ² each independently represent a substituted or unsubstituted alkylene group or a substituted or unsubstituted silylene group, at least one of which is a substituted or unsubstituted alkylene group, M ¹ is titanium, Zirconium or hafnium is shown, and X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryloxy group. ]

[0014]

Embedded image

In the formula (2), A^ThreeAre each independently cyclo
Pentadienyl group, substituted cyclopentadienyl group, in
A benzyl group or a substituted indenyl group,
At least pentadienyl group and substituted indenyl group
Also has one unsubstituted moiety; ^ThreeIs replaced or omitted
Z represents a substituted alkylene group or a silylene group;¹Is
O, S, NR, PR or CR_TwoOr OR, S
R, NR_TwoOr PR_Two(R is a hydrogen atom, a halogen atom,
C1-C20 hydrocarbon group, C1-C20 halogen
Containing a hydrocarbon group or a heteroatom having 1 to 20 carbon atoms.
A group, and when there are a plurality of Rs,
Neutral two-electron donor selected from (can be different)
A sex ligand, M¹Is titanium, zirconium or ha
X represents funium and X¹, X^TwoIs independently a hydrogen atom,
Halogen atom, alkyl group, alkoxy group or aryl
Represents a ruoxy group. ]

[0016]

Embedded image

[In the formula (3), A ⁴ and A ⁵ each independently represent a cyclopentadienyl group, a substituted cyclopentadienyl group,
Represents an indenyl group or a substituted indenyl group, but has at least one unsubstituted moiety in a substituted cyclopentadienyl group or a substituted indenyl group; Y ⁴ represents a substituted or unsubstituted alkylene group; M ¹ represents titanium; Zirconium or hafnium is shown, and X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryloxy group. [6] The above-mentioned [3] to [3], wherein the cocatalyst of the component (B) is any of alumoxane, boroxane, borate, ionic compound, Lewis acid or clay or a mixture thereof.
The α-olefin-styrene copolymer according to any one of [5].

[7] The α-olefin-aromatic vinyl compound copolymer according to any one of the above [1] to [6], wherein the aromatic vinyl compound is styrene.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a copolymer comprising an α-olefin and an aromatic vinyl compound as described above,
An α-olefin-aromatic compound copolymer having a low alternating property and a high blocking property, particularly a high blocking property caused by an aromatic vinyl compound. Thereby, the mechanical strength is further improved as compared with the conventional product, and the properties of the comonomer can be sufficiently brought out.

The α-olefin-aromatic vinyl compound copolymer of the present invention (hereinafter, also referred to as the copolymer of the present invention) will be described in detail. The α-olefin-aromatic vinyl compound copolymer of the present invention is a copolymer comprising an α-olefin and an aromatic vinyl compound, wherein the content of the aromatic vinyl compound is 0.1 to 90 mol% and GPC The molecular weight distribution measured by the method is 3.0 or less, and ¹³
In the C-NMR measurement, a signal (Sβ) based on an (aromatic vinyl compound-olefin-olefin) chain
δ), a signal (Sββ) based on the (aromatic vinyl compound-olefin-aromatic vinyl compound) chain is present,
Further, a signal (Tββ) based on a block chain of an aromatic vinyl compound (aromatic vinyl compound-aromatic vinyl compound-aromatic vinyl compound) and a block chain of an olefin portion (olefin-olefin-olefin). The signal (Sδδ) is present, and the index (θ) indicating the blocking property of the aromatic vinyl compound component represented by the following relational expression is 10 to 80 (%).

[0021]

(Equation 3)

[Wherein I (Tββ + Tβδ) is ¹³ C
In NMR measurement, the sum of the intensities of the signals Tββ and Tβδ is shown. Here, Tβδ indicates a signal based on a (aromatic vinyl compound-aromatic vinyl compound-olefin) chain. I (Tδδ + Tγδ + Tββ + Tβ
δ) is a signal Tδδ, Tγδ, Tββ, Tβδ based on all the chains involving the aromatic vinyl compound component in the chain of the copolymer in the ¹³ C-NMR measurement.
Shows the sum of the respective intensities. Here, Tδδ is a signal based on the (olefin-aromatic vinyl compound-olefin) chain, and Tγδ is a signal based on a heterogeneous bond of the (aromatic vinyl compound-aromatic vinyl compound-olefin-olefin) chain or (aromatic vinyl compound). -Olefin-aromatic vinyl compound-olefin). The α-olefin-aromatic vinyl compound copolymer of the present invention is a copolymer composed of an α-olefin and an aromatic vinyl compound. It contains. This means
^This is supported by the presence of Sβδ based on the (aromatic vinyl compound-olefin-olefin) chain and Sββ based on the (aromatic vinyl compound-olefin-aromatic vinyl compound) chain in the ¹³ C-NMR measurement.

The copolymer of the present invention further comprises ¹³ C-NMR
In the measurement, a signal (Tββ) based on a block chain of an aromatic vinyl compound (aromatic vinyl compound−aromatic vinyl compound−aromatic vinyl compound) and a block chain of an olefin portion (olefin−olefin−
Olefin) (Sδδ).
With these, it is possible to further improve the mechanical strength as compared with the conventional product, and it is possible to sufficiently bring out the properties of the comonomer.

Further, the copolymer of the present invention has a high blocking property, particularly a high blocking property of the aromatic vinyl compound component, and is an index (θ:) indicating the blocking property of the aromatic vinyl compound component represented by the above relational formula. Hereinafter, also referred to as block index) is 10 to 80 (%), preferably 10 to 70 (%).
(%). If θ is less than 10 (%), the blocking property is too low to improve the mechanical strength. On the other hand, if it exceeds 80 (%), the balance between flexibility and mechanical strength is reduced.

In the above formula, I (Tββ + Tβδ) is
^{In 13} C-NMR measurement, signals Tββ and Tβδ
Shows the sum of the intensities of Here, Tβδ indicates a signal based on a (aromatic vinyl compound-aromatic vinyl compound-olefin) chain. Therefore, both of these signals indicate that the blocking property of the aromatic vinyl compound is strongly reflected. On the other hand, I (Tδδ + T
γδ + Tββ + Tβδ) are the signals Tδδ, Tγ based on all the chains involving the aromatic vinyl compound component in the chains of the copolymer in the ¹³ C-NMR measurement.
The sum of the respective intensities of δ, Tββ, and Tβδ is shown. Here, Tδδ is a signal based on a (olefin-aromatic vinyl compound-olefin) chain, and Tγδ is a signal based on a heterogeneous bond of an (aromatic vinyl compound-aromatic vinyl compound-olefin-olefin) chain or (aromatic vinyl compound). -Olefin-aromatic vinyl compound-olefin). The above-mentioned hetero bond means that a head-to-head bond or a tail-to-tail bond is formed with respect to a head-to-tail bond which is a usual method of bonding monomers.

In the measurement of ¹³ C-NMR in the present invention, lambda 500 manufactured by JEOL Ltd. was used. A sample was placed in an NMR tube having a diameter of 1 cm, and 1,2,4-trichlorobenzene / deuterated benzene was used. After adding 3 ml of a 9/1 solvent, heating and dissolving at 140 ° C., the temperature is increased to 130 ° C.

The copolymer of the present invention has an aromatic vinyl compound content of 0.1 to 90 mol%, but may have any content within this range. If it is less than 0.1 mol%, the mechanical strength cannot be improved. On the other hand, if it exceeds 90 mol%, the balance between flexibility and mechanical strength is reduced.

The copolymer of the present invention has a molecular weight distribution represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by the GPC method of 3.0 or less, preferably 1 or less. 0.5 to 3.0. The molecular weight distribution is measured by gel permeation chromatography (GPC). GPC measurement conditions are as follows: GPC column Shod
Using ex UT806L, temperature 145 ° C, solvent 1,
2,4-trichlorobenzene, flow rate 1.0 ml / mi
n. Measure with. If the molecular weight distribution is 3.0 or more, stickiness occurs and moldability and surface characteristics are reduced.

The stereoregularity of the copolymer of the present invention is not particularly limited, but a copolymer having an atactic stereocyclicity of an aromatic ring in a chain of aromatic vinyl compound components in a polymer chain is more flexible. This is preferable in a field where such properties are required, for example, a film / sheet field using a soft vinyl chloride resin. The stereoregularity can be measured, for example, using ¹³ C-NMR.

The weight average molecular weight of the copolymer of the present invention is usually from 1,000 to 1,000 in terms of polystyrene.
It is 0000, preferably 5,000 to 800,000, but can be appropriately selected within this range as needed.

The copolymer of the present invention is a copolymer composed of an α-olefin and an aromatic vinyl compound. It may be a ternary or quaternary copolymer containing a cyclic olefin and / or a diene.

Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,
Decene, 4-phenyl-1-butene, 6-phenyl-1
-Hexene, 3-methyl-1-butene, 4-methyl-1
-Butene, 3-methyl-1-pentene, 4-methyl-1
-Pentene, 3-methyl-1-hexene, 4-methyl-
1-hexene, 5-methyl-1-hexene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, vinylcyclohexane, hexafluoropropene, tetra Fluoroethylene, 2-fluoropropene, fluoroethylene, 1,
Preferred examples include 1-difluoroethylene, 3-fluoropropene, trifluoroethylene, and 3,4-dichloro-1-butene.

As the aromatic vinyl compound, styrene, p-methylstyrene, p-ethylstyrene, p-ethylstyrene,
Propylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, o-methylstyrene, o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-propylstyrene, m-
Alkyl styrenes such as isopropyl styrene, m-butyl styrene, mesityl styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene and 3,5-dimethyl styrene; p-methoxy styrene, o-methoxy styrene, m-methoxy Alkoxystyrenes such as styrene;
p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene,
o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p
Halogenated styrenes such as -fluorostyrene; more preferably, p-phenylstyrene, trimethylsilylstyrene, vinyl benzoate, divinylbenzene and the like.

Examples of the cyclic olefin include cyclopentene, cyclohexene, norbornene, 1-methylnorbornene, 5-methylnorbornene, 7-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5-phenylnorbornene and 5-benzylnorbornene. , 5,6-dimethylnorbornene, 5,
Suitable examples include 5,6-trimethylnorbornene.

Further, as the diene, 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene and the like are used. The above-mentioned α-olefins, aromatic vinyl compounds, cyclic olefins, and dienes may be used alone or in combination of two or more.

As the α-olefin-aromatic vinyl compound copolymer of the present invention, specifically, ethylene-styrene copolymer, propylene-styrene copolymer, butene-
1-styrene copolymer and the like. These α-
The content of the aromatic vinyl compound in the olefin-aromatic vinyl compound-based copolymer is 0.1 to 90 mol%, but may be any content within this range. For example, the content of the aromatic vinyl compound is preferably low in order to secure the same flexibility as a soft vinyl chloride resin, for which the development of an alternative resin is called out due to environmental problems. Specifically, 0.
It is 1 to 30 mol%, preferably 1 to 30 mol%, particularly preferably 10 to 30 mol%. On the other hand, when importance is placed on mechanical strength, the content of the aromatic vinyl compound is preferably high. Specifically, 35 to 90 mol%, preferably 4
0 to 90 mol%.

Examples of the terpolymer comprising an α-olefin, an aromatic vinyl compound and a cyclic olefin or diene include, for example, ethylene-styrene-norbornene copolymer, ethylene-styrene-butadiene copolymer and ethylene-styrene. Styrene-1,5-hexadiene copolymer and the like can be mentioned. A structural unit derived from an α-olefin in a polymer chain such as an α-olefin-aromatic vinyl compound-cyclic olefin copolymer or an α-olefin-aromatic vinyl compound-diene copolymer; and an aromatic vinyl compound. The ratio of the structural unit derived from the compound and the structural unit derived from the cyclic olefin or diene can be any ratio. In particular, the content of the aromatic vinyl compound is 50 mol% or less, and the content of the cyclic olefin or diene is Is preferably 20 mol% or less, which is a copolymer having high elastic recovery and being highly practical.

The method for producing the α-olefin-aromatic vinyl compound copolymer of the present invention includes (A) a transition metal compound component and (B) a co-catalyst component, and if necessary,
As a catalyst component, a method of copolymerizing an α-olefin and an aromatic vinyl compound in the presence of a polymerization catalyst comprising a polymerization catalyst obtained by adding an alkylating agent (C) is exemplified. Examples of the transition metal compound of the component (A) include compounds represented by the following general formulas (1), (2) and (3).

[0039]

Embedded image

[In the formula (1), A ¹ and A ² each independently represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group;
Y ¹ and Y ² each independently represent a substituted or unsubstituted alkylene group or a substituted or unsubstituted silylene group, at least one of which is a substituted or unsubstituted alkylene group, M ¹ is titanium, Zirconium or hafnium is shown, and X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryloxy group. ]

[0041]

Embedded image

[In the formula (2), A^ThreeAre each independently cyclo
Pentadienyl group, substituted cyclopentadienyl group, in
A benzyl group or a substituted indenyl group,
At least pentadienyl group and substituted indenyl group
Also has one unsubstituted moiety; ^ThreeIs replaced or omitted
Z represents a substituted alkylene group or a silylene group;¹Is
O, S, NR, PR or CR_TwoOr OR, S
R, NR_TwoOr PR_Two(R is a hydrogen atom, a halogen atom,
C1-C20 hydrocarbon group, C1-C20 halogen
Containing a hydrocarbon group or a heteroatom having 1 to 20 carbon atoms.
A group, and when there are a plurality of Rs,
Neutral two-electron donor selected from (can be different)
A sex ligand, M¹Is titanium, zirconium or ha
X represents funium and X¹, X^TwoIs independently a hydrogen atom,
Halogen atom, alkyl group, alkoxy group or aryl
Represents a ruoxy group. ]

[0043]

Embedded image

[In the formula (3), A^Four, A^FiveAre independent of each other.
Clopentadienyl group, substituted cyclopentadienyl group,
Shows an indenyl group or a substituted indenyl group.
Less in clopentadienyl and substituted indenyl groups
Having at least one unsubstituted moiety,^FourIs replaced or
Represents an unsubstituted alkylene group;¹Is titanium, zirconi
Or hafnium, and X¹, X^TwoAre independent
A hydrogen atom, a halogen atom, an alkyl group, an alkoxy group
Or an aryloxy group. And a transition metal compound represented by the general formula (1)
In the formula, Y ¹And Y^TwoAt least one of the frames
The bridging group is a cross-linking group consisting only of carbon-carbon bonds.
Titanium conversion having such a chemical structure is important
Specific examples of the compounds include, for example, (isopropyl
Den) (dimethylsilylene) bis (cyclopentadiene)
Le) titanium dichloride, (isopropylidene) (di
Methylsilylene) bis (cyclopentadienyl) titani
Dimethyl, (isopropylidene) (dimethylsilyl
N) bis (cyclopentadienyl) titanium dibenzyl
, (Isopropylidene) (dimethylsilylene) bis
(Cyclopentadienyl) titanium diphenyl, (a
Sopropylidene) (dimethylsilylene) bis (cyclope)
Antadienyl) titanium dimethoxide,
Riden) (dimethylsilylene) bis (cyclopentadie)
Nyl) titanium diphenoxide, (isopropylidide)
) (Dimethylsilylene) bis (cyclopentadienyl)
Le) titanium bis (trimethylsilyl), (isopro
Pyridene) (dimethylsilylene) bis (cyclopentadi)
Enyl) titanium bis (trimethylsilylmethyl),
(Isopropylidene) (dimethylsilylene) bis (sic)
Lopentadienyl) titanium bis (trifluorometa)
Sulfonate), (isopropylidene) (dimethyl
Rylene) bis (cyclopentadienyl) titaniumdihi
Dolide, (isopropylidene) (dimethylsilylene) bi
(Cyclopentadienyl) titanium dichloride
Lido, (isopropylidene) (dimethylsilylene) bis
(Cyclopentadienyl) titanium dichloride methoxide
Sid, (1,1'-isopropylidene) (2,2'-di
Methylsilylene) bis (4-methylcyclopentadieni)
Le) titanium dichloride, (1,1'-isopropyl)
Den) (2,2'-dimethylsilylene) bis (3,5-
Dimethylcyclopentadienyl) titanium dichloride
, (1,1'-isopropylidene) (2,2'-dimethyl
Tylsilylene) bis (3,4,5-trimethylcyclope
(Antadienyl) titanium dichloride, (1,1'-a
Sopropylidene) (2,2'-dimethylsilylene) bis
(3,4-dimethylcyclopentadienyl) titanium
Dichloride, (1,1'-isopropylidene) (2,
2'-dimethylsilylene) bis (3,4-diethylcyclo)
Lopentadienyl) titanium dichloride, (1,1 '
-Isopropylidene) (2,2'-dimethylsilylene)
Bis (3,4-diisopropylcyclopentadienyl)
Titanium dichloride, (1,1'-isopropylide
) (2,2'-dimethylsilylene) bis (3,4-di
-N-butylcyclopentadienyl) titanium dichloro
Lido, (1,1'-isopropylidene) (2,2'-di
Methylsilylene) bis (3,4-di-tert-butyl)
Cyclopentadienyl) titanium dichloride, (1,
1'-isopropylidene) (2,2'-dimethylsilyl)
N) Bis (3,4-diphenylcyclopentadienyl)
Titanium dichloride, (1,1'-isopropylide
) (2,2'-dimethylsilylene) bis (3,4-di
Benzylcyclopentadienyl) titanium dichloride
, (2,2'-isopropylidene) (1,1'-dimethyl
Tylsilylene) bis (indenyl) titanium dichloride
, (1,2'-isopropylidene) (2,1'-dimethyl
Tylsilylene) bis (indenyl) titanium dichloride
, (2,2'-isopropylidene) (1,1'-dimethyl
Tylsilylene) bis (tetrahydroindenyl) titani
Um dichloride, (2,2'-isopropylidene)
(1,1'-dimethylsilylene) bis (3-methylin
(Denyl) titanium dichloride, (2,2'-isopro
Pyridene) (1,1'-dimethylsilylene) bis (3-
Isopropylindenyl) titanium dichloride,
(2,2'-isopropylidene) (1,1'-dimethyl
(Silylene) bis (3-n-butylindenyl) titanium
Mudichloride, (2,2'-isopropylidene) (1,
1'-dimethylsilylene) bis (3-tert-butyl
Indenyl) titanium dichloride, (2,2'-iso
Propylidene) (1,1'-dimethylsilylene) bis
(3-phenylindenyl) titanium dichloride,
(2,2'-isopropylidene) (1,1'-dimethyl
Silylene) bis (3-benzylindenyl) titanium
Dichloride, (2,2'-isopropylidene) (1,
1'-dimethylsilylene) bis (4,7-dimethylin
(Denyl) titanium dichloride, (2,2'-isopro
Pyridene) (1,1′-dimethylsilylene) bis (3,
4,7-trimethylindenyl) titanium dichloride
, (2,2'-isopropylidene) (1,1'-dimethyl
Tylsilylene) bis (5,6-dimethylindenyl) thio
Thanium dichloride, (2,2'-isopropylidene)
(1,1'-dimethylsilylene) bis (4-phenyli
Ndenyl) titanium dichloride, (2,2'-isoprop)
Ropylidene) (1,1'-dimethylsilylene) bis (5
-Phenylindenyl) titanium dichloride, (2,
2'-isopropylidene) (1,1'-dimethylsilyl)
N) Bis (6-phenylindenyl) titanium dichloro
Lido, (2,2'-isopropylidene) (1,1'-di
Methylsilylene) bis (4-phenyl-7-methylin
(Denyl) titanium dichloride, (2,2'-isopro
Pyridene) (1,1′-dimethylsilylene) bis (4,
5-benzoindenyl) titanium dichloride, (2,
2'-isopropylidene) (1,1'-dimethylsilyl)
N) bis (5,6-benzoindenyl) titanium
Loride, (2,2'-isopropylidene) (1,1'-
Dimethylsilylene) bis (6,7-benzoindenyl)
Titanium dichloride, (1,1'-isopropylide
) (2,2'-dimethylsilylene) (4-methylcyclyl)
Lopentadienyl) (3 ', 5'-dimethylcyclopen
Tadienyl) titanium dichloride, (1,1'-iso
Propylidene) (2,2'-dimethylsilylene) (4-
Methylcyclopentadienyl) (3 ', 5'-diisoprop
Ropylcyclopentadienyl) titanium dichloride,
(1,1'-isopropylidene) (2,2'-dimethyl
Silylene) (4-methylcyclopentadienyl)
(3 ', 5'-diphenylcyclopentadienyl) tita
Ium dichloride, (1,1'-isopropylidene)
(2,2′-dimethylsilylene) (4-tert-butyl)
Rucyclopentadienyl) (3 ', 5'-dimethylcyclyl)
Lopentadienyl) titanium dichloride, (1,1 '
-Isopropylidene) (2,2'-dimethylsilylene)
(4-phenylcyclopentadienyl) (3 ', 5'-
Dimethylcyclopentadienyl) titanium dichloride
, (1,1'-isopropylidene) (2,2'-dimethyl
Tylsilylene) (cyclopentadienyl) (3 ′, 4 ′
-Dimethylcyclopentadienyl) titanium dichloride
, (1,1'-isopropylidene) (2,2'-dimethyl
Tylsilylene) (cyclopentadienyl) (3 ′, 4 ′
-Diisobutylcyclopentadienyl) titanium dic
Loride, (1,1'-isopropylidene) (2,2'-
Dimethylsilylene) (3,4-dimethylcyclopentadi
Enyl) (3 ', 5'-diphenylcyclopentadienyl
Le) titanium dichloride, (1,1'-isopropyl)
Den) (2,2'-dimethylsilylene) (3,4-dimension
Tylcyclopentadienyl) (3 ′, 5′-diisopro
Pyrcyclopentadienyl) titanium dichloride,
(1,1'-isopropylidene) (2,2'-dimethyl
Silylene) (3,4-dimethylcyclopentadienyl)
(3 ', 5'-diphenylcyclopentadienyl) tita
Ium dichloride, (2,2'-isopropylidene)
(1,1'-dimethylsilylene) (cyclopentadienyl
Le) (indenyl) titanium dichloride, (ethyl
) (Dimethylsilylene) bis (cyclopentadienyl)
Le) titanium dichloride, (2,2'-ethylene)
(1,1'-dimethylsilylene) bis (indenyl) thio
Titanium dichloride, (1,2'-ethylene) (2,
1'-dimethylsilylene) bis (indenyl) titanium
Mudichloride, bis (isopropylidene) bis (cyclo
Pentadienyl) titanium dichloride, ethylene (a
Sopropylidene) bis (cyclopentadienyl) titani
Um dichloride, bis (ethylene) bis (cyclopentane
Dienyl) titanium dichloride, (isopropylidide)
) (Dimethylgermylene) bis (cyclopentadienyl)
Le) titanium dichloride, (1,2'-ethylene)
(2,1'-ethylene) bis (indenyl) titanium
Dichloride, (1,2′-ethylene) (2,1′-ethyl
Len) bis (3-normalbutylindenyl) titanium
Mudichloride, (1,2'-ethylene) (2,1'-e
(Tylene) bis (3-trimethylsilylmethylindeni)
G) titanium dichloride and the like.

It is important that the transition metal compound represented by the general formula (2) has at least one unsubstituted portion in the substituted cyclopentadienyl group and the substituted indenyl group in the formula. Such compounds include dimethylsilylene (tetrahydroindenyl) decylaminotitanium dichloride, dimethylsilylene (tetrahydroindenyl) (trimethylsilylamino) titanium dichloride, dimethylsilylene (2-
Indenyl) (tert-butylamino) titanium dichloride, dimethylsilylene (2-indenyl) (isopropylamino) titanium dichloride, dimethylsilylene (2-indenyl) (benzylamino) titanium dichloride, dimethylsilylene (2-methylbenzoindenyl) ( tert-butylamino) titanium dichloride, isopropylidene (tetrahydroindenyl) decylaminotitanium dichloride, isopropylidene (tetrahydroindenyl) (trimethylsilylamino) titanium dichloride, isopropylidene (2-indenyl) (tert-butylamino) titanium dichloride, Isopropylidene (2-indenyl) (isopropylamino) titanium dichloride, isopropylidene (2-indenyl) Benzylamino) titanium dichloride, isopropylidene (2-methylbenzoindenyl) (tert-butylamino) include titanium dichloride and the like.

It is important that the transition metal compound represented by the general formula (3) has at least one unsubstituted moiety in the substituted cyclopentadienyl group and the substituted indenyl group in the formula. Examples of suitable compounds include methylenebiscyclopentadienyl titanium dichloride, rac-methylenebis (indenyl) titanium dichloride, rac-ethylenebis (indenyl) titanium dichloride, rac-methylenebis (indenyl) titanium chlorohydride, ethylenebiscyclopentadienyltitanium Dichloride, rac-ethylenebis (indenyl) methyltitanium chloride,
rac-ethylenebis (indenyl) methoxychlorotitanium, rac-ethylenebis (indenyl) titaniumdiethoxide, rac-ethylenebis (indenyl) dimethyltitanium, rac-ethylenebis (4,
5,6,7-tetrahydroindenyl) titanium dichloride, rac-ethylenebis (2-methylindenyl) titanium dichloride, rac-ethylenebis (2,4-dimethylindenyl) titanium dichloride, rac-ethylenebis (2- Methyl-4-trimethylsilylindenyl) titanium dichloride, ethylene (2,4-dimethylcyclopentadienyl) (3 ′,
5′-dimethylcyclopentadienyl) titanium dichloride, ethylene (2-methyl-4-tert-butylcyclopentadienyl) (3′-tert-butyl-
5′-methylcyclopentadienyl) titanium dichloride, ethylene (2,3,5-trimethylcyclopentadienyl) (2 ′, 4 ′, 5′-trimethylcyclopentadienyl) titanium dichloride, isopropylidenebiscyclopenta Dienyl titanium dichloride, isopropylidene (cyclopentadienyl) (indenyl)
Titanium dichloride, rac-isopropylidenebis (2-methylindenyl) titanium dichloride, ra
c-isopropylidenebis (indenyl) titanium dichloride, rac-isopropylidenebis (2,4-dimethylindenyl) titanium dichloride, rac-isopropylidenebis (4,5-benzoindenyl) titanium dichloride, isopropylidene (2 4-dimethylcyclopentadienyl) (3′5′-dimethylcyclopentadienyl) titanium dichloride, isopropylidene (2-methyl-4-tert-butylcyclopentadienyl) (3′-tert-butyl-5 ′) -Methylcyclopentadienyl) titanium dichloride, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) titanium dichloride, methylene (cyclopentadienyl) (3,4-dimethylcyclopentadienyl) titanium K Rohidorido, methylene (cyclopentadienyl) (3,4-dimethyl cyclopentadienyl) dimethyl titanium, methylene (cyclopentadienyl) (3,4-dimethyl cyclopentadienyl)
Diphenyltitanium, methylene (cyclopentadienyl) (trimethylcyclopentadienyl) titanium dichloride, methylene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride,
Isopropylidene (cyclopentadienyl) (3,4-
Dimethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride, isopropylidene (cyclopentadienyl) (3-
Methylindenyl) titanium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (2-methylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl) ) (3,4-dimethylcyclopentadienyl) titanium dichloride, isopropylidene (2,5
-Dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (cyclopentadienyl) (2,4-dimethylcyclopentadienyl) titanium dichloride, ethylene (cyclopentadienyl)
(Fluorenyl) titanium dichloride, ethylene (2,5-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (2,5-diethylcyclopentadienyl) (fluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3,4-diethylcyclopentadienyl)
Titanium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, cyclohexylidene (2,5-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) titanium dichloride and the like can be mentioned. Can be

In addition, in these transition metal compounds, titanium is replaced by zirconium or hafnium, or a chlorine atom in chloride is replaced by
These bromides or iodides substituted by bromine atoms or iodine atoms may be used. These transition metal compounds may be used alone or in a combination of two or more.

Next, as the cocatalyst of the component (B) in the catalyst used in the present invention, alumoxane, boroxane, borate, ionic compound, Lewis acid or clay or a mixture thereof can be used. Particularly preferred among these compounds are alumoxanes and borates.

The alumoxane is not particularly limited, and examples thereof include methylalumoxane, ethylalumoxane, butylalumoxane, isobutylalumoxane, tetramethyldialumoxane, tetraethyldialumoxane, and tetraisobutyldialumoxane. It is mentioned as a thing.

Preferred examples of the boroxane include methylboroxane and trimethylboroxine. Further, as the borate, triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate ( n-butyl) ammonium, triethylammonium hexafluoroarsenate, pyridinium tetrakis (pentafluorophenyl) borate, pyrrolium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl)
N, N-dimethylanilinium borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, ferrocenium tetraphenylborate, dimethylferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluoroborate) Phenyl) decamethylferrocenium borate, acetylferrocenium tetrakis (pentafluorophenyl) borate, formylferrocenium tetrakis (pentafluorophenyl) borate, cyanoferosenium tetrakis (pentafluorophenyl) borate, silver tetraphenylborate, Silver tetrakis (pentafluorophenyl) borate, trityl tetraphenylborate, trityl tetrakis (pentafluorophenyl) borate, hexaf Oro arsenic, silver hexafluoroantimonate, silver, etc. silver tetrafluoroborate and the like as preferred.

Examples of the ionic compound include silver trifluoromethanesulfonate and magnesium perchlorate. Preferred examples of Lewis acids include tris (pentafluorophenyl) boron, tris (heptafluoronaphthalinyl) boron, bis (pentafluorophenyl) boron fluoride, and tris (diisobutylaminoxy) borane.

Next, as the above-mentioned clays, natural or artificially synthesized clays, clay minerals and ion-exchangeable layered compounds can be used. These clays are aggregates of fine hydrated silicate minerals that have plasticity when mixed with an appropriate amount of water, exhibit rigidity when dried, and have the property of sintering when baked at high temperatures Clay mineral is a hydrated silicate which is the main component of clay. Further, the ion-exchangeable layered compound is a compound having a crystal structure in which surfaces constituted by ionic bonds and the like are stacked in parallel with a weak binding force to each other, the ions contained therein are exchangeable, and Some are ion-exchangeable layered compounds. Examples of these ion-exchange layered compounds include ionic crystalline compounds having a layered crystal structure such as a hexagonal close-packed type, an antimony type, a cadmium chloride type, and a cadmium iodide type.

Of these clays, clay minerals, and ion-exchangeable layered compounds, particularly preferred are clay minerals such as kaolin mineral, serpentine and related minerals, pyrophyllite, talc, mica clay mineral, chlorite, and vermiculite. , Smectite, mixed layer minerals, sepiolite, palygorskite, allophane, imogolite, Kibushi clay, gairome clay, hisingelite, nacrite and the like. Smectite is more preferable, and among them, montmorillonite, saponite, or hectorite can be suitably used.

When these clays, clay minerals or ion-exchangeable layered compounds are used as the cocatalyst of the component (B) used in the present invention, they are chemically treated and then treated with an organic silane compound or the like. Is preferably used.

As a method of the chemical treatment, for example, a method such as an acid treatment, an alkali treatment, a salt treatment, and an organic substance treatment can be used. In the case of this acid treatment, a method using hydrochloric acid, sulfuric acid or the like is preferable.
The surface area can be increased by removing impurities on the surface and eluting cations such as aluminum, iron and magnesium in the crystal structure of the clay. In the case of alkali treatment, a method using an aqueous solution of sodium hydroxide, aqueous ammonia or the like is preferable, whereby the crystal structure of clays can be changed to a preferable form. In the salt treatment, magnesium chloride or aluminum chloride is used, and in the organic treatment, a method using an organic aluminum, a silane compound, an ammonium salt, or the like is preferable. In the case of treatment with these salts or organic substances, an ion complex, a molecular complex, an organic complex, or the like can be formed, and the surface area, the interlayer distance, and the like can be changed to a preferable form. For example, by using the ion exchange property to replace the exchangeable ions between the layers with another bulky ion, an interlayer material in which the layers are expanded can be obtained. In this case, the clays used as the raw materials may be used as they are for chemical treatment, may be newly added water to which water is adsorbed, or may be those that have been subjected to heat dehydration in advance. You may.

The clays thus chemically treated are:
A treatment with an organic silane compound or the like is performed. Examples of the organic silane compound suitable for this treatment include trialkylsilyl chlorides such as trimethylsilyl chloride, triethylsilyl chloride, triisopropylsilyl chloride, tert-butyldimethylsilyl chloride, tert-butyldiphenylsilyl chloride, and phenethyldimethylsilyl chloride. Dialkylsilyl dichlorides such as dimethylsilyl dichloride, diethylsilyl dichloride, diisopropylsilyl dichloride, bisdiphenethylsilyl dichloride, methylphenethylsilyl dichloride, diphenylsilyl dichloride, dimesitylsilyl dichloride, ditolylsilyl dichloride; methylsilyl trichloride; Ethylsilyl trichloride, isopropylsilyl trichloride, phenylsilyl trichloride, Alkylsilyl trichlorides such as tylsilyl trichloride, tolysilyl trichloride, and phenethylsilyl trichloride; and halides in which the above chloride is replaced by another halogen element; bis (trimethylsilyl) amine, bis (triethylsilyl) amine , Bis (triisopropylsilyl) amine, bis (dimethylethylsilyl) amine, bis (diethylmethylsilyl) amine, bis (dimethylphenylsilyl) amine, bis (dimethyltolylsilyl) amine, bis (dimethylmesitylsilyl) amine, Silylamines such as N, N-dimethylaminotrimethylsilane, (diethylamino) trimethylsilane, N- (trimethylsilyl) imidazole; polysilanos which are commonly called peralkylpolysiloxypolyols Le acids; Tris silanols such as (trimethylsiloxy) silanol, N, O-
Bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, N- (trimethylsilyl) acetamide, bis (trimethylsilyl)
Silylamides such as urea and trimethylsilyldiphenylurea; linear siloxanes such as 1,3-dichlorotetramethyldisiloxane; cyclic siloxanes such as pentamethylcyclopentanesiloxane; dimethyldiphenylsilane, diethyldiphenylsilane, diisopropyldiphenylsilane and the like Tetraalkylsilanes; trimethylsilane, triethylsilane, triisopropylsilane, tri-t-butylsilane, triphenylsilane,
Suitable examples include trialkylsilanes such as tritolylsilane, trimesitylsilane, methyldiphenylsilane, dinaphthylmethylsilane, and bis (diphenyl) methylsilane.

Among these organic silane compounds, those having at least one alkyl group directly bonded to a silicon atom are preferred, and alkylsilyl halides, particularly dialkylsilyl halides, are suitably used. These organic silane compounds may be used alone or in an appropriate combination of two or more.

When the above-mentioned clays are treated with these organic silane compounds, the treatment with the organic silane compounds can be effectively performed by conducting the treatment in the presence of water. In this case, the water breaks the crystal structure (particularly, the laminated structure) of the clays, and acts to increase the contact efficiency between the organosilane compound and the clays. In other words, this water expands between the layers of the clay crystals,
It promotes the diffusion of the organosilane compound. Therefore,
In the treatment of clays with organosilane compounds, the presence of water is important and it is advantageous to increase the amount of water. The amount of water added is 1% by mass or more, preferably 10% by mass or more, and more preferably 100% by mass or more, based on the dry mass of the raw material component of the clays. The dry mass of the raw material component of the clay was calculated by placing the raw material component of the clay in a muffle furnace, heating the mixture to 150 ° C. in 30 minutes, and holding the mixture at 150 ° C. for 1 hour. That is.

As the water used here, it is convenient to use the water originally contained in the clay raw material as it is in operation, but when newly adding water, the clay is suspended in the water. It may be turbid or suspended in a mixed solution of water and an organic solvent. As such an organic solvent, alcohols, esters, ethers, halogenated hydrocarbons, aliphatic hydrocarbons, aromatic hydrocarbons and the like can be used.

The contact treatment of these clays with an organosilane compound may be performed in the air, but is more preferably performed in an inert gas stream such as argon or nitrogen. And the use ratio of the organic silane compound used for this treatment is
The number of moles of silicon atoms in the organosilane compound per 1 kg of the clay may be 0.001 to 1,000, preferably 0.01 to 100.

The catalyst used in the present invention is the above (A)
The transition metal compound of the component and the co-catalyst of the component (B) are essential components, and a catalyst obtained by adding an alkylating agent as the component (C) may be used. As the alkylating agent, an organic aluminum compound, an organic magnesium compound, or an organic zinc compound is used.

Examples of the organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, trin-propylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, trit-butylaluminum, and the like; Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, din-butylaluminum chloride, diisobutylaluminum chloride and di-t-butylaluminum chloride; dimethylaluminum methoxide, dimethylaluminum Dialkyl aluminum alkoxides such as ethoxide; Chill aluminum hydride,
Suitable examples include dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

Further, as the organomagnesium compound,
Dimethyl magnesium, diethyl magnesium, di-n-
Propyl magnesium, diisopropyl magnesium and the like are preferably used. Preferred examples of the organic zinc compound include dimethyl zinc, diethyl zinc, di-n-propylethyl zinc, diisopropyl zinc, and the like.

Next, when preparing a catalyst using each of the above catalyst components, it is desirable to carry out the contacting operation in an atmosphere of an inert gas such as nitrogen gas. Each of these catalyst components may be prepared in advance in a catalyst preparation tank, or may be used as it is in a polymerization reactor for copolymerizing an α-olefin or an aromatic vinyl compound. It may be used for polymerization.

Next, a copolymer of an α-olefin and an aromatic vinyl compound or a cyclic olefin and / or a diene is added to an α-olefin and an aromatic vinyl compound using the polymerization catalyst obtained as described above. To produce a ternary or quaternary copolymer.

The α-olefin, aromatic vinyl compound, cyclic olefin, and diene used in the production of these copolymers include those exemplified above.

Next, bulk polymerization or solution polymerization can be suitably employed as a polymerization system for producing the α-olefin-aromatic vinyl compound copolymer. Solvents used in the case of solution polymerization include, for example, aliphatic hydrocarbons such as butane, pentane and hexane; alicyclic hydrocarbons such as cyclohexane; benzene, toluene,
An aromatic hydrocarbon such as xylene or a liquefied α-olefin is used. The polymerization temperature is not particularly limited, but is usually -50 to 250C, preferably 0 to 200C.
It can be performed in the range of ° C. The pressure during the polymerization is from normal pressure to 20 MPa, preferably from normal pressure to 10 MPa.
Range.

In the copolymerization of these α-olefins with an aromatic vinyl compound or further with a cyclic olefin or diene, a chain transfer agent may be used as the component (D) together with the above catalyst. As such a chain transfer agent, silanes such as silane, phenylsilane, methylsilane, ethylsilane, butylsilane, octylsilane, diphenylsilane, dimethylsilane, diethylsilane, dibutylsilane, dioctylsilane, and hydrogen are preferably used. These may be used alone or in combination of two or more.

[0069]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Example 1 180 ml of toluene, 200 ml of styrene, and 1.0 ml of a 1.0 M toluene solution of triisobutylaluminum were sequentially charged into a 1.6-liter autoclave equipped with a catalyst introduction tube, and the temperature was raised to 50 ° C. . Then, ethylene was changed to 0.3 MPa
・ Introduced in G. Next, a mixture of 10.0 micromoles of (isopropylidene) (dimethylsilylene) bis (cyclopentadienyl) titanium dichloride and 10.0 millimoles of methylalumoxane dissolved in 20 milliliters of toluene was charged from a catalyst charging tube. Polymerization was performed for 1 hour while continuously supplying ethylene so as to maintain a pressure of 0.3 MPa · G. Thereafter, the polymerization was stopped by adding methanol. The polymer was separated by filtration by adding a large amount of methanol, and dried at 60 ° C. under reduced pressure for 4 hours. As a result, 12 g of an ethylene-styrene copolymer was obtained. When measured by GPC-FT / IR shown below,
The weight average molecular weight was 9,200 in terms of polystyrene, and the molecular weight distribution was 2.1. When ¹³ C-NMR was measured by the method described in the specification, the styrene content was 5%.
3.7 mole percent. ¹³ C-NMR obtained
The chart is shown in FIG. (Measurement by GPC-FT / IR) Measurement equipment GPC column oven GPC-FTIR Nicolet MAGNA-IR 650 SPECTROMETER data analysis software OMNIC SEC-FTIR Ver. 2.10.2 Software Measurement conditions Solvent 1,2,4 Trichlorobenzene Temperature 145 ° C Flow rate 1.0ml / min Sample concentration 0.3 (w / v)% Column Shodex UT806MLT 2 molecular weight is PS converted molecular weight. The signal appearing at 29.46 ppm is due to the long chain of the methylene carbon, and when the ethylene unit is represented by E, the methylene carbon derived from the EEE chain (Sδ
δ).

The signal appearing at 45.69 ppm is
Tδδ carbons based on heterogeneous bonds in the (ethylene-styrene-ethylene) chain and (ethylene-styrene-styrene-
It is assigned to a Tγδ carbon based on an (ethylene) chain. Three
The signal appearing at 6.69 ppm is assigned to the Sαγ carbon based on the (ethylene-styrene-ethylene) chain. The signal appearing at 27.37 ppm is assigned to Sβδ based on the (styrene-ethylene-ethylene) linkage. (Tδδ + Tγδ), the area intensity ratio of each of Sαγ and Sβδ is approximately 1: 2: 2, and a signal derived from a long chain of methylene carbon is observed at 29.46 ppm as described above. Is represented by S, there is an S / E chain structure I as shown below.

[0071]

Embedded image

The signal appearing at 25.21 ppm is due to the Sββ carbon from the SES linkage in S / E linkage structure II as shown below.

[0073]

Embedded image

The signal appearing at 34.61 ppm is the signal derived from the inversion bond of styrene represented by the following structure.
It is considered to be a signal due to αβ carbon.

[0075]

Embedded image

Signal appearing at 44.29 ppm and 4
Signals appearing at 1.05 ppm are assigned to Sαα carbon and Tββ carbon, respectively. These are signals derived from the styrene-styrene triad chain.

Based on the above assignments, Tδδ, Tδ
The sum I (Tδδ + Tγδ + Tββ + Tβδ) of the respective signal intensities of γδ, Tββ, and Tβδ, and Tβ
β, the sum of the signal intensities of Tβδ, I (Tββ
+ Tβδ), and the calculated block index (θ) was 29%. Table 1 shows the above results.

In the calculation of the intensity, (Tδ
δ + Tγδ) is a signal appearing from 45 ppm to 46.5 ppm, and Tββ is a signal appearing from 41 ppm to 41.5 pp.
m, the Tβδ is 43 ppm to 44
The signals appearing in ppm were each targeted. Comparative Example 1 180 ml of toluene, 200 ml of styrene, and 1.0 ml of a 1.0 M toluene solution of triisobutylaluminum were sequentially charged into a 1.6-liter autoclave equipped with a catalyst introduction tube, and the temperature was raised to 50 ° C. . Then, ethylene was changed to 0.3 MPa
・ Introduced in G. Then, a mixture of 10.0 mmol of methylalumoxane and 10.0 μmol of bis (dimethylsilylene) biscyclopentadienylzirconium dichloride dissolved in 20 ml of toluene was introduced from a catalyst introduction tube. Ethylene pressure 0.3MPa · G
The polymerization was carried out for 1 hour while continuously supplying so as to maintain the temperature. Thereafter, the polymerization was stopped by adding methanol. The polymer was separated by filtration by adding a large amount of methanol, and dried at 60 ° C. under reduced pressure for 4 hours. As a result, 11 g of an ethylene-styrene copolymer was obtained.

Thereafter, the same procedure as in Example 1 was performed. That is, as measured by GPC-FT / IR, the weight average molecular weight was 16,400 in terms of polystyrene, and the molecular weight distribution was 2.0. ^As determined by ¹³ C-NMR, the styrene content was 22.3 mole percent. In addition,
1C shows ¹³ C-NMR of the polymer. Styrene-
No Tββ signal due to triad linkage of styrene was seen. The calculated block index (θ) was 0%. Table 1 shows the above results. Example 2 200 ml of styrene and 1.0 ml of a 1.0 M toluene solution of triisobutylaluminum were sequentially charged into a 1.6-liter autoclave equipped with a catalyst introduction tube, and the temperature was raised to 50 ° C. Then, ethylene was introduced at 0.1 MPa · G. Then, 50.0 micromoles of (2-methylbenzoindenyl) (t-butylamido) dimethylsilanetitanium dichloride dissolved in 20 milliliters of toluene were added through a catalyst charging tube.
A mixture of 0.0 mmol of methylalumoxane was charged. Polymerization was carried out for 2 hours while continuously supplying ethylene so as to maintain a pressure of 0.1 MPa · G. afterwards,
The polymerization was stopped by the addition of methanol. The polymer was separated by filtration by adding a large amount of methanol, and dried at 60 ° C. under reduced pressure for 4 hours. As a result, 38.6 g of an ethylene-styrene copolymer was obtained.

Thereafter, the same procedure as in Example 1 was performed. That is, as measured by GPC-FT / IR, the weight average molecular weight was 210,000 in terms of polystyrene, and the molecular weight distribution was 2.1. ^As determined by ¹³ C-NMR, the styrene content was 61.8 mol%. Also,
FIG. 2 shows the ¹³ C-NMR of the polymer. 44.29pp
As can be seen from the signal appearing at m and the signal appearing at 41.05 ppm, signals of Sαα carbon and Tββ carbon derived from the styrene-styrene triad chain were observed. Further, the calculated block index (θ) was 19%. Table 1 shows the above results. Comparative Example 2 180 ml of toluene, 200 ml of styrene, and 1.0 ml of a 1.0 M toluene solution of triisobutylaluminum were sequentially charged into a 1.6-liter autoclave equipped with a catalyst introduction tube, and the temperature was raised to 50 ° C. . Then, ethylene was changed to 0.3 MPa
・ Introduced in G. Then, a mixture of 10.0 mmol of methylalumoxane and 10.0 μmol of (tetramethylcyclopentadienyl) (t-butylamido) dimethylsilanetitanium dichloride dissolved in 20 ml of toluene was introduced from a catalyst introduction tube. Polymerization was carried out for 10 minutes while continuously supplying ethylene so as to maintain a pressure of 0.3 MPa · G. Thereafter, the polymerization was stopped by adding methanol. The polymer was separated by filtration by adding a large amount of methanol, and dried at 60 ° C. under reduced pressure for 4 hours.
As a result, 38.8 g of an ethylene-styrene copolymer was obtained.

Thereafter, the same procedure as in Example 1 was performed. That is, as measured by GPC-FT / IR, the weight average molecular weight was 260,000 in terms of polystyrene, and the molecular weight distribution was 2.7. The styrene content was 36.7 mole percent. FIG. 3 shows ¹³ C-NMR of the polymer. No Tββ signal due to the styrene-styrene triad chain was seen. The calculated block index (θ) was 0%. Table 1 shows the above results.

[0082]

[Table 1]

[0083]

According to the present invention, an α-olefin-aromatic vinyl compound copolymer composed of structural units having a low alternating property and a high block property, particularly a novel copolymer having a high block property of an aromatic vinyl compound component, is provided. A polymer is provided. This may improve the mechanical strength of the α-olefin-aromatic vinyl compound copolymer.

[Brief description of the drawings]

FIG. 1 shows ¹³ C of the ethylene-styrene copolymer of Example 1.
FIG. 9 is an NMR (A) and ¹³ C-NMR (B) of the ethylene-styrene copolymer of Comparative Example 1. FIG.

FIG. 2 shows ¹³ C of the ethylene-styrene copolymer of Example 2.
-NMR.

FIG. 3 shows ¹³ C of ethylene-styrene copolymer of Comparative Example 2.
-NMR.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 214/18 C08F 214/18 F term (Reference) 4J028 AA01A AB01A AC01A AC08A AC10A AC26A AC27A BA00A BA01B BA02B BB00A BB01B BB02B BC05B BC09B BC12B BC15B BC16B BC24B BC25B BC27B CA30C EB01 EB02 EB04 EB05 EB07 EB08 EB09 EB10 EB13 EB16 EB21 EB22 EC02 FA01 FA02 FA09 GA06 4J100 AA02P AA03P AA04P AA07P AA09P AA15P AA16P AA17P AA18P AA19P AA20P AA21P AB00P AB02Q AB04Q AB07Q AB08Q AB09Q AB10Q AC02P AC22P AC23P AC25P AC26P AC27P BA05Q BA72Q BC43Q CA04 DA04

Claims (7)

[Claims] 1. A copolymer comprising an α-olefin and an aromatic vinyl compound, wherein the content of the aromatic vinyl compound is 0.1 to 90 mol% and the molecular weight distribution measured by the GPC method is 3.0 or less. In the ¹³ C-NMR measurement, the signal (Sβδ) based on the (aromatic vinyl compound-olefin-olefin) chain and the signal (Sββ) based on the (aromatic vinyl compound-olefin-aromatic vinyl compound) chain are A signal (Tββ) based on a block chain of an aromatic vinyl compound (aromatic vinyl compound-aromatic vinyl compound-aromatic vinyl compound), and a block chain of an olefin portion (olefin-olefin-olefin) ), And a block of the aromatic vinyl compound component represented by the following relational expression: Index (θ) indicating the property is 1
Α-olefin-aromatic vinyl compound copolymer having 0 to 80 (%). (Equation 1) [Wherein I (Tββ + Tβδ) indicates the sum of the intensities of the signals Tββ and Tβδ in ¹³ C-NMR measurement. Here, Tβδ indicates a signal based on a (aromatic vinyl compound-aromatic vinyl compound-olefin) chain. I (Tδδ + Tγδ + Tββ + Tβδ) is ¹³ C
In the NMR measurement, the sum of the respective intensities of the signals Tδδ, Tγδ, Tββ, and Tβδ based on all the chains involving the aromatic vinyl compound component in the chains of the copolymer is shown. However, Tδδ is a signal based on the (olefin-aromatic vinyl compound-olefin) chain,
Tγδ is (aromatic vinyl compound-aromatic vinyl compound-
3 shows a signal based on a hetero bond of an (olefin-olefin) chain or a signal based on a hetero bond of an (aromatic vinyl compound-olefin-aromatic vinyl compound-olefin) chain. ] 2. The α-olefin-aromatic vinyl compound copolymer according to claim 1, wherein the aromatic ring in the chain of the aromatic vinyl compound component in the copolymer is atactic. 3. The method according to claim 1, wherein an α-olefin and an aromatic vinyl compound are copolymerized in the presence of a polymerization catalyst comprising (A) a transition metal compound component and (B) a cocatalyst component. Α-olefin-aromatic vinyl compound copolymer. 4. The component (A) and the component (B) according to claim 3.
The α catalyst according to claim 3, wherein a polymerization catalyst obtained by adding an alkylating agent (C) as a catalyst component in addition to the component is used.
-An olefin-aromatic vinyl compound copolymer. 5. The method according to claim 1, wherein the component (A) in the polymerization catalyst is
Transition gold represented by the general formula (1), (2) or (3)
The α- according to claim 3 or 4, which is any one of the genus compounds.
Olefin-aromatic vinyl compound copolymer. Embedded image[In the formula (1), A¹, A^TwoAre each independently cyclopentane
Dienyl group, substituted cyclopentadienyl group, indenyl
A group or a substituted indenyl group,¹, Y^TwoAre each
Independently substituted or unsubstituted alkylene group or substituted
Or unsubstituted silylene groups, of which at least
Is a substituted or unsubstituted alkylene group;
¹Represents titanium, zirconium or hafnium;
¹, X^TwoIs independently a hydrogen atom, a halogen atom,
Represents a kill group, an alkoxy group or an aryloxy group.
You. [Chemical formula 2][In the formula (2), A^ThreeAre each independently cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group or
Represents a substituted indenyl group, but is a substituted cyclopentadienyl
At least one non-substituent in a substituted or indenyl group
Having a replacement part, Y ^ThreeIs substituted or unsubstituted alkylene
Z or a silylene group;¹Is O, S, N
R, PR or CR_TwoOr OR, SR, NR_Twoor
Is PR_Two(R is a hydrogen atom, a halogen atom, carbon number 1 to
20 hydrocarbon groups, halogen-containing carbon atoms having 1 to 20 carbon atoms
A hydrogen group or a heteroatom-containing group having 1 to 20 carbon atoms;
And when there are a plurality of R,
A neutral two-electron donating ligand selected from
And M¹Is titanium, zirconium or hafnium
And X¹, X^TwoAre each independently a hydrogen atom or a halogen
Atom, alkyl group, alkoxy group or aryloxy
Represents a group. [Chemical formula 3][In the formula (3), A^Four, A^FiveAre each independently cyclopentadi
Enyl group, substituted cyclopentadienyl group, indenyl group
Or a substituted indenyl group, but
At least one of an enyl group and a substituted indenyl group;
Having an unsubstituted moiety, Y^FourIs a substituted or unsubstituted al
Represents a kylene group;¹Is titanium, zirconium or ha
X represents funium and X¹, X^TwoIs independently a hydrogen atom,
Halogen atom, alkyl group, alkoxy group or aryl
Represents a ruoxy group. ] 6. The co-catalyst of the component (B) is alumoxane,
4. A boroxane, borate, ionic compound, Lewis acid or clay or a mixture thereof.
5. The α-olefin-styrene copolymer according to any one of 5. 7. The α-olefin-aromatic vinyl compound copolymer according to claim 1, wherein the aromatic vinyl compound is styrene.